Intramolecular Bromoamination of Conjugated N-Tosylaminodienes Using N-Bromosuccinimide. Synthesis of Bromoallyl-Substituted N-Heterocycles and Their Applications as Building Blocks

The bromonium-promoted cyclization of conjugated aminodienes is described. The reaction proceeds smoothly in the presence of N-bromosuccinimide as halonium promoter, and using N-tosyl-protected aminodienes as substrates, to give the corresponding halocyclization products in high yields and with high diastereoselectivities. It can be envisaged that the formation of these products is the result of an SN2′-type ring-opening of a terminal bromonium intermediate in a 5-exo-trig or 6-exo-trig cyclization mode. The presence of an allyl bromide moiety in the haloamination products makes these molecules highly attractive from a synthetic point of view, as it opens the way for further transformations. Thus, allylic substitution reactions with different nucleophiles (acetate, azide, cyanide, and malonate), palladium-catalysed Suzuki coupling, and silver-mediated bromine displacement reactions were carried out successfully.

Comparison of Lattice-Fluid Binary Parameters For Mixtures and Block Copolymers

The aim of this report is to discuss the method of determination of lattice-fluid binary interaction parameters by comparing well characterized immiscible blends and block copolymers of poly(methyl methacrylate) (PMMA) and poly(ϵ−caprolactone) (PCL). Experimental pressure-volume-temperature (PVT) data in the liquid state were correlated with the Sanchez—Lacombe (SL) equation of state with the scaling parameters for mixtures and copolymers obtained through combination rules of the characteristic parameters for the pure homopolymers. The lattice-fluid binary parameters for energy and volume were higher than those of block copolymers implying that the copolymers were more compatible due to the chemical links between the blocks. Therefore, a common parameter cannot account for both homopolymer blend and block copolymer phase behaviors based on current theory. As we were able to adjust all data of the mixtures with a single set of lattice-binary parameters and all data of the block copolymers with another single set we can conclude that both parameters did not depend on the composition for this system. This characteristic, plus the fact that the additivity law of specific volumes can be suitably applied for this system, allowed us to model the behavior of the immiscible blend with the SL equation of state. In addition, a discussion on the relationship between lattice-fluid binary parameters and the Flory–Huggins interaction parameter obtained from Leibler's theory is presented.

1,3-Dipolar cycloadditions of azomethine imines

Azomethine imines are considered 1,3-dipoles of the aza-allyl type which are transient intermediates and should be generated in situ but can also be stable and isolable compounds. They react with electron-rich and electron-poor olefins as well as with acetylenic compounds and allenoates mainly by a [3 + 2] cycloaddition but they can also take part in [3 + 3], [4 + 3], [3 + 2 + 2] and [5 + 3] with different dipolarophiles. These 1,3-dipolar cycloadditions (1,3-DC) can be performed not only under thermal or microwave conditions but also using metallo- and organocatalytic systems. In recent years enantiocatalyzed 1,3-dipolar cycloadditions have been extensively considered and applied to the synthesis of a great variety of dinitrogenated heterocycles with biological activity. Acyclic azomethine imines derived from mono and disubstituted hydrazones could be generated by prototropy under heating or by using Lewis or Brønsted acids to give, after [3 + 2] cycloadditions, pyrazolidines and pyrazolines. Cyclic azomethine imines, incorporating a C–N bond in a ring, such as isoquinolinium imides are the most widely used dipoles in normal and inverse-electron demand 1,3-DC allowing the synthesis of tetrahydro-, dihydro- and unsaturated pyrazolo[1,5-a]isoquinolines in racemic and enantioenriched forms with interesting biological activity. Pyridinium and quinolinium imides give the corresponding pyrazolopyridines and indazolo[3,2-a]isoquinolines, respectively. In the case of cyclic azomethine imines with an N–N bond incorporated into a ring, N-alkylidene-3-oxo-pyrazolidinium ylides are the most popular stable and isolated dipoles able to form dinitrogen-fused saturated and unsaturated pyrazolopyrazolones as racemic or enantiomerically enriched compounds present in many pharmaceuticals, agrochemicals and other useful chemicals.

Technologies for Seduction: The “Espacio Doméstico” VideoArt Center in Blanca [EDOM]

Sustainability, understood in its beginnings as a common horizon for multiple practices and fields of study, has gradually given way to the development of increasingly sophisticated tools, with distinct dominant meanings established for each discipline. Within the field of material technologies for architectural production, sustainability seems to have found its most fertile ground in topics such as recycling, the use of "bio" materials, or energetic efficiency. However, to improve the understanding of the impact of technology on our ways of living, it appears increasingly necessary to move from the deterministic logic of sustainability into the relational domain of ecology, where the use and deployment of technologies can be observed through the multiplicity of its effects and the diversity of actors involved. In this paper we will address the case of the rehabilitation of several traditional houses located in the Murcian town of Blanca to host the “Espacio Doméstico” VideoArt Center (EDOM). In this action the selection and implementation of technologies have been aimed at impacting on diverse aspects including local communities, digital manufacturing, recycling, and policies regarding the rehabilitation of heritage buildings. While the initial approach was to address housing recovery as a heterogeneous accumulation of stories, technologies or material deployments of the domestic, our intervention strategies ascribed to the different technologies the role of mediating with existing elements through the incorporation of the very different visions of sustainability. Thus, we displayed artifacts produced by digitally manufactured methacrylate assembled on IKEA structures, fluorescent power lines supported by insulators on the wall, fluorescent tattoos on walls and ceilings that guide and extend the configuration of existing flooring, esparto furniture and fabrics produced by the esparto women workers’ and village women’s associations, re-appropriations of old furniture through the implementation of new media technologies, etc. If we can see seduction as the process of converting affinities and disagreements into affirmative communication, then the EDOM proposal can be seen as an active seduction process between technologies and users who approach this kind of cultural artifacts. Through these permanently active processes, art technologies will refer the viewer to complex sensory experiences, where a combination of parody, memory and sound pushes the user to the limit of mere comprehension of works of art. This more relational approach to the issue of heritage rehabilitation, technology or art institutions is offered as an area of controversy and debate on the scope of political ecology and its potential impact on the architect’s professional practice.